CN112095167A - Method for regulating and controlling luminous fiber spectrum behavior by using phosphomolybdic acid - Google Patents
Method for regulating and controlling luminous fiber spectrum behavior by using phosphomolybdic acid Download PDFInfo
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- CN112095167A CN112095167A CN202010918545.6A CN202010918545A CN112095167A CN 112095167 A CN112095167 A CN 112095167A CN 202010918545 A CN202010918545 A CN 202010918545A CN 112095167 A CN112095167 A CN 112095167A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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Abstract
The invention provides a method for regulating and controlling luminous fiber spectrum behaviors by using phosphomolybdic acid, which comprises the following steps: (1) preparing the rare earth luminescent material modified by organic silicon resin; (2) adding the rare earth luminescent material modified by the organic silicon resin into a solid solution consisting of phosphomolybdic acid and polyvinyl alcohol, stirring in a constant-temperature water bath after ultrasonic dispersion, adjusting the pH value to be acidic, performing suction filtration and washing for multiple times by using absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the phosphomolybdic acid; (3) and preparing the phosphomolybdic acid modified noctilucent fiber. The luminescent fiber modified by the phosphomolybdic acid has double emission spectrums which are respectively positioned at 438nm and 520nm, the wavelength is positioned in a blue area about 480nm after the double spectrums are overlapped, the light color generates blue shift relative to the luminescent fiber before the phosphomolybdic acid is modified, the application field of the luminescent fiber is expanded, and the luminescent fiber can be used for blue light material products, in addition, the luminescent fiber after the phosphomolybdic acid is modified can continuously emit light for more than 10 hours in a dark state after absorbing visible light for 10 minutes.
Description
Technical Field
The invention relates to the technical field of functional fibers, in particular to a method for regulating and controlling spectral behaviors of noctilucent fibers by using phosphomolybdic acid.
Background
The rare earth strontium aluminate luminescent material is a light-storing high-tech functional material, the luminescent fiber which is widely applied at present mainly adopts the rare earth strontium aluminate luminescent material as a luminescent light source, the luminescent performance is better, but the luminescent spectrum is mainly concentrated in a 520nm yellow-green light area, and the light color is single and lacks diversity. Although the luminous spectrum of the noctilucent fiber can be regulated and controlled to a certain degree by adding the inorganic transparent pigments with different colors into the spinning raw material of the noctilucent fiber, researches show that the addition of the inorganic transparent pigments can finally cause the afterglow brightness of the noctilucent fiber to be greatly reduced, the service life to be shortened and the application to be limited. Therefore, the finding of a material capable of regulating the spectrum of the noctilucent fiber is a problem which is generally concerned at present.
Disclosure of Invention
The invention aims to disclose a method for regulating spectral behavior of a noctilucent fiber by using phosphomolybdic acid, which is respectively positioned at 438nm and 520nm, the wavelength of the overlapped double spectra is positioned in a blue region of about 480nm, the light color generates blue shift relative to the noctilucent fiber before phosphomolybdic acid modification, the application field of the noctilucent fiber is expanded, the noctilucent fiber can be used for blue light material products, in addition, the noctilucent fiber after phosphomolybdic acid modification absorbs visible light for 10 minutes and can continuously emit light for more than 10 hours in a dark state, the afterglow brightness of the noctilucent fiber cannot be reduced due to phosphomolybdic acid modification, and the service life is.
In order to achieve the purpose, the invention provides a method for regulating and controlling the spectrum behavior of a noctilucent fiber by using phosphomolybdic acid, which comprises the following steps:
(1) dispersing the rare earth luminescent powder into absolute ethyl alcohol, adding organic silicon resin after ultrasonic dispersion, magnetically stirring, carrying out suction filtration and washing for multiple times by using the absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the organic silicon resin;
(2) adding the rare earth luminescent material modified by the organic silicon resin into a solid solution consisting of phosphomolybdic acid and polyvinyl alcohol, stirring in a constant-temperature water bath after ultrasonic dispersion, adjusting the pH value to be acidic, performing suction filtration and washing for multiple times by using absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the phosphomolybdic acid;
(3) the luminescent fiber is prepared by taking rare earth luminescent material modified by phosphomolybdic acid and polymer as raw materials and performing melt spinning.
In some embodiments, in the step (1), the weight ratio of the rare earth luminescent powder, the anhydrous ethanol and the silicone resin is 1-2: 10-12: 0.01 to 0.03.
In some embodiments, in step (1), the rare earth luminescent powder is prepared from SrAl2O 4: eu2+ and Dy3+ luminescent powder.
In some embodiments, in step (1), the silicone resin is an aminosilicone resin.
In some embodiments, in step (2), the molar ratio of phosphomolybdic acid to polyvinyl alcohol is 1: 180-220, wherein the weight ratio of the solid solution to the rare earth luminescent material is 1-3: 1.
in some embodiments, in step (2), the pH is adjusted to 3 by the dropwise addition of 2mol/L acetic acid.
In some embodiments, in step (2), the particle size of the rare earth luminescent material modified by phosphomolybdic acid is less than or equal to 10 μm.
In some embodiments, in the step (1), the ultrasonic dispersion time is 20-40 min, the magnetic stirring time is 3-5h, the drying temperature is 80-100 ℃, and the drying time is 20-25 h; in the step (2), the ultrasonic dispersion time is 20-40 min, the temperature of the constant-temperature water bath is 50-70 ℃, the stirring time is 3-5h, the drying temperature is 80-100 ℃, and the drying time is 20-25 h.
In some embodiments, in the step (3), the weight ratio of the rare earth luminescent material modified by phosphomolybdic acid to the polymer is 1-2: 2 to 10.
In some embodiments, in the step (3), the rare earth luminescent material modified by phosphomolybdic acid and the slice-dried polymer are mixed in a melt spinning machine, extruded by a twin-screw extruder at a melting temperature of 220 ℃ to 280 ℃, and finally drawn and wound to form the noctilucent fiber.
Compared with the prior art, the invention has the beneficial effects that: the luminescent fiber modified by the phosphomolybdic acid has double emission spectrums which are respectively positioned at 438nm and 520nm, the wavelength is positioned in a blue region about 480nm after the double spectrums are overlapped, the light color generates blue shift relative to the luminescent fiber before the phosphomolybdic acid modification, the application field of the luminescent fiber is expanded, and the luminescent fiber can be used for blue light material products.
Drawings
FIG. 1 is a scanning electron microscope image of a rare earth strontium aluminate luminescent material before phosphomolybdic acid modification;
FIG. 2 is a scanning electron microscope image of a rare earth strontium aluminate luminescent material modified by phosphomolybdic acid;
FIG. 3 is an electron microscope image of a luminescent fiber modified by phosphomolybdic acid;
FIG. 4 is an emission spectrum of a luminescent fiber modified by phosphomolybdic acid;
FIG. 5 is an emission spectrum of a luminescent fiber before phosphomolybdic acid modification;
FIG. 6 is a CIE 1931 chromaticity diagram;
FIG. 7 is a graph showing afterglow luminance of luminescent fibers before and after phosphomolybdic acid modification.
Detailed Description
The present invention is described in detail with reference to the embodiments shown in the drawings, but it should be understood that these embodiments are not intended to limit the present invention, and those skilled in the art should understand that functional, methodological, or structural equivalents or substitutions made by these embodiments are within the scope of the present invention.
Example one：
The embodiment discloses a method for regulating and controlling luminous fiber spectrum behaviors by using phosphomolybdic acid, which comprises the following steps:
(1) dispersing the rare earth luminescent powder into absolute ethyl alcohol, adding organic silicon resin after ultrasonic dispersion, magnetically stirring, carrying out suction filtration and washing for 3 times by using the absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the organic silicon resin.
Wherein the weight ratio of the rare earth luminescent powder to the absolute ethyl alcohol to the organic silicon resin is 1: 10: 0.01. the rare earth luminescent powder is prepared from SrAl2O 4: eu2+ and Dy3+ luminescent powder. The organic silicon resin is amino organic silicon resin. The ultrasonic dispersion time is 20min, the magnetic stirring time is 3h, the drying temperature is 80 ℃, and the drying time is 20 h.
(2) Adding the rare earth luminescent material modified by the organic silicon resin into a solid solution consisting of phosphomolybdic acid and polyvinyl alcohol, stirring in a constant-temperature water bath after ultrasonic dispersion, adjusting the pH value to be acidic, performing suction filtration and washing for 3 times by using absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the phosphomolybdic acid.
Wherein the molar ratio of the phosphomolybdic acid to the polyvinyl alcohol is 1: 180, the weight ratio of the solid solution to the rare earth luminescent material is 1: 1. the pH was adjusted to 3 by dropwise addition of 2mol/L acetic acid. The ultrasonic dispersion time is 20min, the temperature of the constant temperature water bath is 50 ℃, the stirring time is 3h, the drying temperature is 80 ℃, and the drying time is 20 h. The particle size of the rare earth luminescent material modified by phosphomolybdic acid is less than or equal to 10 mu m, and the rare earth luminescent material is convenient to use for spinning.
(3) The luminescent fiber is prepared by taking rare earth luminescent material modified by phosphomolybdic acid and polymer as raw materials and performing melt spinning.
Wherein, the weight ratio of the rare earth luminescent material modified by phosphomolybdic acid to the polymer is 1: 2. mixing the rare earth luminescent material modified by phosphomolybdic acid and the polymer after slicing and drying in a melt spinning machine, extruding the mixture by a double-screw extruder at the melting temperature of 220 ℃, and finally drafting and winding the mixture to obtain the noctilucent fiber.
Example two：
The embodiment discloses a method for regulating and controlling luminous fiber spectrum behaviors by using phosphomolybdic acid, which comprises the following steps:
(1) dispersing the rare earth luminescent powder into absolute ethyl alcohol, adding organic silicon resin after ultrasonic dispersion, magnetically stirring, carrying out suction filtration and washing for 3 times by using the absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the organic silicon resin.
Wherein the weight ratio of the rare earth luminescent powder to the absolute ethyl alcohol to the organic silicon resin is 1.5: 11: 0.02. the rare earth luminescent powder is prepared from SrAl2O 4: eu2+ and Dy3+ luminescent powder. The organic silicon resin is amino organic silicon resin. The ultrasonic dispersion time is 30min, the magnetic stirring time is 4h, the drying temperature is 90 ℃, and the drying time is 24 h.
(2) Adding the rare earth luminescent material modified by the organic silicon resin into a solid solution consisting of phosphomolybdic acid and polyvinyl alcohol, stirring in a constant-temperature water bath after ultrasonic dispersion, adjusting the pH value to be acidic, performing suction filtration and washing for 3 times by using absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the phosphomolybdic acid.
Wherein the molar ratio of the phosphomolybdic acid to the polyvinyl alcohol is 1: 200, solid solution and rare earth luminescent material weight ratio of 2: 1. the pH was adjusted to 3 by dropwise addition of 2mol/L acetic acid. The ultrasonic dispersion time is 30min, the temperature of the constant-temperature water bath is 60 ℃, the stirring time is 4h, the drying temperature is 90 ℃, and the drying time is 24 h. The particle size of the rare earth luminescent material modified by phosphomolybdic acid is less than or equal to 10 mu m, and the rare earth luminescent material is convenient to use for spinning.
(3) The luminescent fiber is prepared by taking rare earth luminescent material modified by phosphomolybdic acid and polymer as raw materials and performing melt spinning.
Wherein, the weight ratio of the rare earth luminescent material modified by phosphomolybdic acid to the polymer is 1.5: 6. mixing the rare earth luminescent material modified by phosphomolybdic acid and the polymer after slicing and drying in a melt spinning machine, extruding the mixture by a double-screw extruder at the melting temperature of 260 ℃, and finally drafting and winding the mixture to obtain the noctilucent fiber.
EXAMPLE III：
The embodiment discloses a method for regulating and controlling luminous fiber spectrum behaviors by using phosphomolybdic acid, which comprises the following steps:
(1) dispersing the rare earth luminescent powder into absolute ethyl alcohol, adding organic silicon resin after ultrasonic dispersion, magnetically stirring, carrying out suction filtration and washing for 3 times by using the absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the organic silicon resin.
Wherein the weight ratio of the rare earth luminescent powder to the absolute ethyl alcohol to the organic silicon resin is 2: 12: 0.03. the rare earth luminescent powder is prepared from SrAl2O 4: eu2+ and Dy3+ luminescent powder. The organic silicon resin is amino organic silicon resin. The ultrasonic dispersion time is 40min, the magnetic stirring time is 5h, the drying temperature is 100 ℃, and the drying time is 25 h.
(2) Adding the rare earth luminescent material modified by the organic silicon resin into a solid solution consisting of phosphomolybdic acid and polyvinyl alcohol, stirring in a constant-temperature water bath after ultrasonic dispersion, adjusting the pH value to be acidic, performing suction filtration and washing for 3 times by using absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the phosphomolybdic acid.
Wherein the molar ratio of the phosphomolybdic acid to the polyvinyl alcohol is 1: 220, solid solution and rare earth luminescent material weight ratio of 3: 1. the pH was adjusted to 3 by dropwise addition of 2mol/L acetic acid. The particle size of the rare earth luminescent material modified by phosphomolybdic acid is less than or equal to 10 mu m. The ultrasonic dispersion time is 40min, the temperature of the constant temperature water bath is 70 ℃, the stirring time is 5h, the drying temperature is 100 ℃, and the drying time is 25 h.
(3) The luminescent fiber is prepared by taking rare earth luminescent material modified by phosphomolybdic acid and polymer as raw materials and performing melt spinning.
Wherein, the weight ratio of the rare earth luminescent material modified by phosphomolybdic acid to the polymer is 1: 5. mixing the rare earth luminescent material modified by phosphomolybdic acid and the polymer after slicing and drying in a melt spinning machine, extruding the mixture by a double-screw extruder at the melting temperature of 280 ℃, and finally drafting and winding the noctilucent fiber.
And (3) analyzing experimental data and results:
as shown in FIGS. 1 to 7, the experiments are conducted on the rare earth strontium aluminate luminescent material and the luminescent fiber in the second embodiment.
Comparing fig. 1 and fig. 2, it can be seen that: the surface of the rare earth strontium aluminate luminescent material modified by the phosphomolybdic acid is smooth, and compared with the rare earth strontium aluminate luminescent material before the phosphomolybdic acid is modified, the rare earth strontium aluminate luminescent material is not aggregated, so that the rare earth strontium aluminate luminescent material is in dispersed arrangement, and the rest brightness is improved and the afterglow time is prolonged.
As can be seen from fig. 3: the diameter of the noctilucent fiber modified by phosphomolybdic acid is about 25 mu m, and granular solids are attached to the surface of the noctilucent fiber and are rare earth strontium aluminate luminescent materials or phosphomolybdic acid solids.
From fig. 4 and 5, it can be derived that: the double-emission spectrum phenomenon of the luminescent fiber modified by the phosphomolybdic acid is generated, the blue shift is generated relative to the light color of the luminescent fiber before the phosphomolybdic acid is modified, and the light color area of the luminescent fiber modified by the phosphomolybdic acid is blue, so that the effect of the phosphomolybdic acid on regulating the spectrum behavior of the luminescent fiber is further verified. In the figure, the abscissa is wavelength in nm and the ordinate is relative intensity in counts.
In fig. 6, (a) is a noctilucent fiber before phosphomolybdic acid modification; (b) is luminous fiber modified by phosphomolybdic acid; (C) is phosphomolybdic acid; (d) the luminous effect of the luminous fiber modified by phosphomolybdic acid under a fluorescence microscope is achieved; the light color of the luminescent fiber modified by the phosphomolybdic acid is generated by superposing the luminescent colors of a yellow-green luminescent center of the luminescent fiber before the phosphomolybdic acid is modified and a blue-violet luminescent center of the phosphomolybdic acid, and the light color matched with yellow-green light and blue-violet light can be obtained by a light color addition principle and belongs to a blue light area, so that the luminescent color spectrum of the luminescent fiber modified by the phosphomolybdic acid is blue, and generates light color blue shift relative to the rare earth strontium aluminate luminescent material before the modification which emits yellow-green light.
As can be seen from FIG. 7, the afterglow luminance curves of the luminescent fibers before and after phosphomolybdic acid modification almost overlap, and it is understood that phosphomolybdic acid modification does not cause decrease in afterglow luminance of the luminescent fibers, and the service life is shortened, and the application is not limited.
The principle of regulating the spectral behavior of the noctilucent fiber by using phosphomolybdic acid is as follows:
phosphomolybdic acid is a polynuclear photosensitive complex with a cage-like structure, and a solid solution formed by phosphomolybdic acid and high polymers such as polyvinyl alcohol, polyvinyl butyral and the like containing side groups in molecules can change color under the action of light or heat. Phosphomolybdic acid with hydroxyl (-OH) or amino (-NH) groups2) The redox reaction easily occurs between organic electron donors of the active groups.
The main reasons why the luminous fiber can emit blue light are: the luminescent fiber modified by phosphomolybdic acid generates intramolecular photoinitiated charge transfer under the irradiation of ultraviolet light or visible light, and Mo appears6+→Mo5+Valence-layer charge transfer transition peak belonging to the characteristic band of heteropolyblue; the rare earth strontium aluminate luminescent material in the noctilucent fiber belongs to energy storage luminescence, so that after the noctilucent fiber receives illumination in a dark state, the phosphomolybdic acid photosensitive material can be used as a luminescent donor part of the noctilucent fiber, d-d electrons contained in molecules of the phosphomolybdic acid photosensitive material are transited to an excited state, the molecules in the excited state can transfer redundant energy to a strontium aluminate luminescent material receptor, due to the specific electronic configuration of rare earth ions, the rare earth strontium aluminate luminescent fiber can spontaneously absorb light energy or receive energy from a phosphomolybdic acid organic system to be transited to the excited state, characteristic fluorescence of each ion is emitted, and different spectra can achieve the purpose of adjusting the spectrum of the rare earth strontium aluminate noctilucent fiber after superposition interference.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for regulating and controlling luminous fiber spectrum behaviors by using phosphomolybdic acid is characterized by comprising the following steps:
(1) dispersing the rare earth luminescent powder into absolute ethyl alcohol, adding organic silicon resin after ultrasonic dispersion, magnetically stirring, carrying out suction filtration and washing for multiple times by using the absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the organic silicon resin;
(2) adding the rare earth luminescent material modified by the organic silicon resin into a solid solution consisting of phosphomolybdic acid and polyvinyl alcohol, stirring in a constant-temperature water bath after ultrasonic dispersion, adjusting the pH value to be acidic, performing suction filtration and washing for multiple times by using absolute ethyl alcohol, and drying to obtain the rare earth luminescent material modified by the phosphomolybdic acid;
(3) the luminescent fiber is prepared by taking rare earth luminescent material modified by phosphomolybdic acid and polymer as raw materials and performing melt spinning.
2. The method for regulating and controlling the spectral behavior of the noctilucent fiber by applying phosphomolybdic acid according to claim 1, wherein in the step (1), the weight ratio of the rare earth luminescent powder, the absolute ethyl alcohol and the organic silicon resin is (1-2): 10-12: 0.01 to 0.03.
3. The method for regulating and controlling the spectral behavior of the noctilucent fiber by using phosphomolybdic acid as claimed in claim 1 or 2, wherein in the step (1), the rare earth luminescent powder is prepared by adopting SrAl2O 4: eu2+ and Dy3+ luminescent powder.
4. The method for regulating the spectral behavior of noctilucent fibers by using phosphomolybdic acid as claimed in claim 1 or 2, wherein in the step (1), the organic silicon resin is amino organic silicon resin.
5. The method for regulating and controlling the spectral behavior of noctilucent fibers by phosphomolybdic acid according to claim 1, wherein in the step (2), the molar ratio of phosphomolybdic acid to polyvinyl alcohol is 1: 180-220, wherein the weight ratio of the solid solution to the rare earth luminescent material is 1-3: 1.
6. the method for regulating the spectral behavior of noctilucent fibers by phosphomolybdic acid according to claim 1, wherein in the step (2), the pH is adjusted to 3 by dripping 2mol/L acetic acid.
7. The method for regulating the spectral behavior of noctilucent fibers by using phosphomolybdic acid as claimed in claim 1, wherein in the step (2), the particle size of the rare earth luminescent material modified by phosphomolybdic acid is less than or equal to 10 μm.
8. The method for regulating the spectrum behavior of the noctilucent fiber by using phosphomolybdic acid according to claim 1, wherein in the step (1), the ultrasonic dispersion time is 20-40 min, the magnetic stirring time is 3-5h, the drying temperature is 80-100 ℃, and the drying time is 20-25 h; in the step (2), the ultrasonic dispersion time is 20-40 min, the temperature of the constant-temperature water bath is 50-70 ℃, the stirring time is 3-5h, the drying temperature is 80-100 ℃, and the drying time is 20-25 h.
9. The method for regulating and controlling the spectral behavior of the noctilucent fiber by using phosphomolybdic acid according to claim 1, wherein in the step (3), the weight ratio of the rare earth luminescent material modified by the phosphomolybdic acid to the polymer is 1-2: 2 to 10.
10. The method for regulating the spectral behavior of the noctilucent fiber by using phosphomolybdic acid according to claim 1 or 9, wherein in the step (3), the rare earth luminescent material modified by phosphomolybdic acid and the polymer after slicing and drying are mixed in a melt spinning machine, extruded by a twin-screw extruder at a melting temperature of 220-280 ℃, and finally, the noctilucent fiber is drawn and wound.
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2020
- 2020-09-04 CN CN202010918545.6A patent/CN112095167A/en not_active Withdrawn
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| GB617080A (en) * | 1946-01-28 | 1949-02-01 | Stevensons Dyers Ltd | Improvements in fastness to light of dyed textile materials |
| CN103469353A (en) * | 2013-09-07 | 2013-12-25 | 河北联合大学 | Preparation method of phosphomolybdic acid/polyacrylic acid/polyvinyl alcohol composite fiber |
| CN103467531A (en) * | 2013-10-10 | 2013-12-25 | 贵州大学 | H3PMo12O40-(HO)10Q[5]-light rare earth metal heterocomplex and synthesis and application |
| CN106012292A (en) * | 2016-06-21 | 2016-10-12 | 安庆市天虹新型材料科技有限公司 | Antibacterial waterproof polyvinyl alcohol nanofiber membrane |
| CN109021964A (en) * | 2018-07-06 | 2018-12-18 | 宁波大学 | A kind of preparation method of organic salt/rare earth aluminic acid strontium composite blue light material |
Non-Patent Citations (1)
| Title |
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| LI JING等: "第2部分第2.1-2.3节", 《PREPARATION AND PHOTOCHROMIC PROPERTIES OF PHOSPHOMOLYBDIC ACID/RARE EARTH STRONTIUM ALUMINATE LUMINOUS FIBER》 * |
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